Laminar thermoplastic films, bags thereof

ABSTRACT

A heat sealable film laminate having a first layer of a major amount of high density polyolefin, a minor proportion of an adhesion promoting ionomer and a heat seal promoting proportion of a metal salt of a fatty acid; and a second layer adhering to the first layer, said layer comprising a polyamide. A food storage and heating bag formed from said laminate and a method of heat sealing said laminate.

BACKGROUND OF THE INVENTION

The present invention relates to coextruded laminar thermoplastic filmsand bag structures formed therefrom. The invention further relates tolaminar film structures comprising two layers of films which are formedfrom dissimilar thermoplastic resins. The invention also relates to amethod of improving the heat seal between face to face layers of thesame layer of the laminar structure.

DESCRIPTION OF THE PRIOR ART

Previously, polyethylene bags have been employed for the storage of foodin its refrigerated condition. This type of container or bag isparticularly convenient for the keeping of food leftovers which areintended for later reheating. The storage bags have been formed fromcomparatively low density polyethylene, i.e., polyethylene having adensity from about 0.910 to about 0.930 g/cc. Bags made from such lowdensity polyethylene do not have utility for holding food or leftoversduring heating because the polyethylene cannot stand cookingtemperatures on the order of 215° F. or greater. Even at temperaturesbelow this, the polyethylene has a tendency to at least partially meltand adhere to the surface of the heating means or vessel.

Attempts have been made to employ polyester bags, such as polyethyleneterephthalate for such elevated temperature applications, however, suchfilms are difficult to seal and are prohibitively expensive for suchdisposable bag applications.

It has been known in the past that laminar film for food packaging maybe formed from a laminate of nylon and polyethylene provided that anadhesive inner layer is provided between the polyethylene and the nylon.Such a construction involves a three layer structure and as suchpresents manufacturing difficulties including the employment of threeseparate extruders in the manufacturing operation to produce a singlefilm. The elimination of the intermediate adhesive layer of such astructure is addressed in U.S. Pat. No. 4,220,664, incorporated hereinby reference in its entirety. While the bag structure described in thispatent is effective as a container which can withstand the temperatureof cooking or reheating, the efficacy of the bag seal regions leavessomething to be desired. U.S. Pat. No. 3,819,792 to Ono et al isdirected to a process for blow molding a laminar layer structurecomposed of a layer of a polyamide and a layer of homopolymer orcopolymer of an olefin and an ethylene/alpha, beta unsaturatedcarboxylic acid copolymer. This patent is not concerned with compositesof improved heat sealability.

SUMMARY OF THE INVENTION

The present invention provides for an economical thermoplastic laminarfilm system, which has a variety of uses, but which is particularly welladapted to be formed into bag structures employed to contain food duringstorage. The same bag may be used during cooking or reheatingpreparatory to serving. The present invention also provides for animproved method of heat sealing the surfaces or the edges of the subjectlaminar film structure.

The heat sealable film laminate of the present invention comprises a twolayer laminar structure comprising a first layer which comprises a highdensity polyolefin containing a minor amount of an adhesion promotingionomer and a heat seal promoting proportion of a metal salt of a fattyacid; and a second layer adhering to said first layer wherein the secondlayer comprises a polyamide. The high density polyolefin has a densityof from about 0.930 to about 0.960 g/cc. The high density polyolefin ispreferably a copolymer of ethylene with less than about 10% by weight ofan alpha-olefin based upon the weight of the copolymer. The alpha-olefincan be present in from about 1 to 8% by weight and especially preferredis about 2 to 6% by weight of the copolymer.

The adhesion promoting ionomer resins are well known in the art and maybe characterized as metal-containing ionic copolymers obtained by thereaction between ethylene or an alpha-olefin with an ethylenicallyunsaturated monocarboxylic acid, such as, acrylic or methacrylic acid,wherein at least 10% of said carboxylic acid groups are neutralized byan alkali metal ion or zinc ion. Such ionomer resins are disclosed inU.S. Pat. No. 3,496,061, the disclosure of which is incorporated hereinby reference. The ionomer resin is present in from about 5% to about 25%by weight of said first layer. Preferably, the ionomer resin is presentin about 10% by weight of the first layer so that the weight ratio isapproximately 9:1. It is preferred that the ionomer contain either asodium or zinc ion. The ionomer functions primarily in promoting theadhesion of the first layer to the polyamide layer. The metal salts of afatty acid contemplated by the present invention can be any one or amixture of alkali metal, alkaline earth metal or zinc salts of a C₁₂-C₁₈ fatty acid. Calcium and/or zinc salts of stearic acid arepreferred.

While it is acknowledged that stearic acid and certain zinc salts havebeen employed on the surface of organic films, in order to takeadvantage of their lubricating characteristics and prevent blockingbetween the surfaces of contacting polymer films, it has been found thatthe homogeneous or uniform dispersion of the above mentioned metal saltsthroughout the first layer of the subject laminar films unexpectedlypromotes effective heat sealing of the first layer of the structure toitself. Thus, with a heat sealing proportion of such a metal salt withinsaid first layer, seals that are formed from a face to face heat seal ofthe first layer are significantly stronger and noticably free of voidsin the seal area. It has been found that generally an adhesion promotingproportion is from about 1000 to about 7500 parts per million of saidfirst layer. A more preferred range is from about 1500 to about 5000 permillion and a particularly prefered proportion is about 2000 parts permillion of said first layer.

The second or polyamide layer of the present invention is preferably anylon. The nylons contemplated include both those prepared bycondensation of a dibasic acid and a diamine and those formed bypolymerization by addition reactions of amine compounds that containboth acid and amine groups on the monomer. Examples of the first typeare nylon-6/6, nylon-6/9, nylon-6/10 and nylon-6/12. An example of nylonpolymerized by the addition reaction of ring compounds and, which isparticularly preferred is nylon-6, polymerized from e-caprolactam toform polycaproamide.

While there is no real limit to the thickness of the laminar film, apreferred range is from about 0.5 to about 10 mils, preferably fromabout 0.75 mils to about 5 mils. Composite film for food bag use will befrom 0.8 to 1.5 mils thick.

The ratio of the polyamide layer to the polyolefin layer, expressed in apercent by weight, is from about 5 to 20% by weight of the polyamidelayer to 80 to 90% by weight of the polyolefin layer. It is preferredthat the polyamide layer be approximately 10% by weight of the overallcomposite. The preferred high density polyethylene is a copolymer ofethylene with less than 10% by weight of an alpha-olefin based upon thecopolymer. The contemplated alpha-olefins are those having from about 3up to about 10 carbon atoms. Particularly preferred are 1-butene;1-hexene, 2-ethyl; 1-hexene; 1-octene; etc.

As indicated above, the laminar thermoplastic structure of the presentinvention is particularly suited for fabrication into bags suited forthe containment of foodstuffs to be heated to a preparation temperature.These bags are generally defined by a structure resulting from foldingthe film to form a generally U-shaped trough and then side sealing bothends of the trough to form a simple bag or pouch. In use, the consumerwill place food to be prepared, or to be reheated, inside of the pouchand close the top by some suitable means, for example a twist tie means.In forming a bag of this type, the polyolefin layer is positioned sothat it is the inner layer of the bag laminate or that surface of thebag which comes into direct contact with the contents thereof. In thisarrangement the outer layer will be the nylon film or that surface whichcomes into direct contact with the cooking or reheating vessel. Theouter nylon film layer maintains the inner, more thermally susceptible,polyethylene layer out of contact with the surfaces of the coolingvessel and hence improves the bags ability to withstand highertemperatures. Nylon-6, for example, has a melting or stickingtemperature on the order of above 210° C. and is stable and will notstick to the vessel side walls while food stuffs are being reheatedtherein. The bag containing foodstuffs is intended to be immersed in afluid such as water during the reheating operation or employed in amicrowave oven.

DESCRIPTION OF SPECIFIC EMBODIMENTS

A tubular thermoplastic laminate was prepared utilizing conventionalblown tubular film coextrusion techniques whereby the material whichforms the inner layer was melt mixed in one heated screw extruder andthe material which forms the outer layer was melt-mixed in an adjacentheated screw extruder. These materials were then coextruded through atypical die arrangement which permitted the formation of the laminartube.

Into the first heated screw extruder, was melt-mixed a high densitypolyethylene-1-octene copolymer, identified by the manufacturer asAlathon 7810, 10% by weight of an ionomer resin, identified by themanufacturer as Surlyn 1652 and 2000 parts per million of calciumstearate based upon the weight of this composition. In the adjacentheated screw extruder was melted nylon-6. The two compositions werecoextruded so a to yield a tube having a wall thickness of approximately1.2 where the outer nylon-6 layer was approximately 0.1 mil thick andthe inner layer of the copolymer, the Surlyn and the calcium stearatewas approximately 1.1 mils thick.

The continuous laminar tube was subsequently converted into bagstructures by collapsing the tube, longitudinally slitting the collapsedtube so as to form a pair of U-shaped film composites, and feeding thesemembers through an FMC Model 106 side seal machine. Simple side sealedpouch bags were formed by melt severing through the U-shaped members.

For comparison purposes an identical film composite was formed with theexception that the calcium stearate was not present in the inner baglayer. In all other respects, the film composite and bag structures wereidentical.

The resin identified by the manufacturer as Alathon 7810 was anethylene-1-octene copolymer with a 1-octene content of about 3% byweight. This material had the following typical properties for a 1.25mil film extruded at a 4.3/1 blow-up ratio:

Density 0.945 g/cc

Melt Index 0.25 g/10 min.

Tensile Yield

(MD): 3,000 psi

(TD): 3,100 psi

Elongation (MD): 660%

(2"/min.)(TD): 730%

Secant Modulus

(MD): 80 M psi

(TD): 82 M psi

Elmendorf Tear

(MD): 45 g/mil

(TD): 247 g/mil

Spencer Impact: 2.8 in. lbs./mil

Dart Drop (26 in.): 115 g/mil

Tear propagation

(MD): 3.2 Kg force

ASTM D-2582 (TD): 3.7 Kg force

The ionomer, identified by the manufacturer as Surlyn 1652, containszinc as the major cation and has the following typical average physicalproperties for a one mil blown film extruded at a 2:1 blow-up ratio:

    ______________________________________                                        FILM PROPERTIES                                                               Property     Value            ASTM Test                                       ______________________________________                                        Density      .939 g/cc        D1505-68                                        Melt Index   4.4 decigm/min   D1238-65T                                       Tensile Strength                                                                           2850 psi         D638-67                                         Tensile Yield                                                                              1870 psi         D-368-67                                        Elongation   580%             D-368-67                                        Elmendorf Tear                                                                             125/140 g/mil (MD/TD)                                                                          D-1922-67                                       Dart Drop (23")                                                                            220 g/mil        D-1709/67                                       ______________________________________                                    

The nylon-6 outer layer was fabricated from a resin identified by themanufacturer as CAPRON 8207 which had the following typical physicalproperties:

Density: 1.13 g/cc

Tensile YIeld: 11,800 psi (ASTM-P-638)

Deflection Temperature: 140° F. (ASTM-D-648 at 264 psi stress)

It had been found that a significant number of the side seals of priorart bags were developing weak portions with bubbles or pores along thefused bead formed during the seal-melt severing step in the bagformation process. It was discovered that in spite of the knownlubricating and anti-stick characteristics of metal salts of fattyacids, such as calcium stearate, when such a metal salt is present inthe first layer of the composite, a significantly more uniform andstrong side seal is obtained. This is shown by the following comparisonwhere one inch wide strips were cut from bags formed as disclosed above.These one inch wide strips contained a heat seal approximately in thecenter section thereof at right angles to the one inch dimension. Themeasuring units employed are percent elongation, which denotes theextent to which the one inch wide strip of film, containing the heatseal, can be elongated before the seal fails. The elongation wasmeasured on a Instron Model No. 1130 tensile testing apparatus.

    ______________________________________                                                    Control    Test Comparison                                                    (No calcium                                                                              (2000 ppm-calcium                                      Sample No.  stearate)  stearate)                                              ______________________________________                                        1           256%       364%                                                   2           225%       302%                                                   3           109%       342%                                                   4           191%       274%                                                   5           191%       306%                                                   ______________________________________                                    

An examination of the seal of the laminar film containing the calciumstearate showed an extremely uniform, pore and bubble free seal bead. Anexamination of the control seals showed the presence of pores or voidswhich apparently permitted the failure of the seal to occur at asignificantly lower elongation point than with the seals containing thecalcium stearate.

While the specific examples show the use of a particularethylene/alpha-olefin copolymer, it is understood that other copolymerswithin the indicated density range can be employed. For instance, anethylene/hexene copolymer having a density of 0.939 g/cc, and availablefrom the manufacture under the name Marlex HHM TR-130, also can beemployed. Likewise, other ionomer resins such as SURLYN 1905, having adensity of 0.94 g/cc and a zinc ion can be employed.

Although the present invention has been described with reference topreferred embodiments, it is to be understood that modifications andvariations may be resorted to without departing from the spirit andscope of this invention. Such modifications and variations areconsidered to be within the purview and scope of the appended claims.

What is claimed is:
 1. A heat sealable film laminate comprising a first layer comprising a major amount of a high density polyolefin, a minor amount of an adhesion promoting ionomer and a heat seal promoting proportion of a metal salt of a fatty acid; and a second layer adhering to said first layer, said second layer comprising a polyamide.
 2. The laminate of claim 1 wherein said polyolefin is a polyethylene polymer having a density of from about 0.930 to about 0.960 g/cc, said minor amount is from about 5% to about 25% by weight of said first layer and said polyamide is a nylon.
 3. The laminate of claim 2 wherein said polyethylene polymer is a copolymer of ethylene and less than 10% by weight of an alpha-olefin based on said copolymer.
 4. The laminate of claim 3 wherein the alpha-olefin has from about 3 to about 10 carbon atoms.
 5. The laminate of claim 4 wherein the alpha-olefin is a member selected from the group consisting of 1-butene; 1-hexene, 2-ethyl; 1-hexene and 1-octene.
 6. The laminate of claim 1 wherein said metal salt of a fatty acid is at least one member selected from the group consisting of alkali metal, alkaline earth metal and zinc salts of a C₁₂ -C₁₈ fatty acid.
 7. The laminate of claim 6 wherein said metal salt is a member selected from the group consisting of calcium and zinc salts of a C₁₂ -C₁₈ fatty acid.
 8. The laminate of claim 7 wherein said salt is a member selected from the group consisting of calcium and zinc stearate.
 9. The laminate of claim 7 wherein said salt is calcium stearate.
 10. The laminate of claim 1 wherein said adhesion promoting proportion is from about 1000 to about 7500 parts per million of said first layer.
 11. The laminate of claim 10 wherein said adhesion promoting proportion is from about 1500 to about 5000 parts per million of said first layer.
 12. The laminate of claim 11 wherein said adhesion promoting proportion is about 2000 parts per million of said first layer.
 13. The laminate of claim 1 wherein said polyolefin is a copolymer of ethylene and a member selected from the group consisting of 1-butene; 1-hexene, 2-ethyl; 1-hexene and 1-octene; said ionomer is a metal-containing ionic copolymer of an olefin and an ethylenically unsaturated monocarboxylic acid; and said polyamide is nylon-6.
 14. A laminar thermoplastic bag, particularly suited for the containment of foodstuffs to be heated to a preparation temperature, which comprises a first layer comprising a major amount of a high density polyolefin, a minor amount of an adhesion promoting ionomer and a heat seal promoting proportion of a metal salt of a fatty acid; a second layer adhering to said first layer and comprising a polyamide; and wherein said bag includes a heat seal between contacted faces of said first layer along at least one edge region of said bag.
 15. The bag of claim 14 wherein said polyolefin is a polyethylene polymer having a density of from about 0.930 to about 0.960 g/cc, said minor amount is from about 5% to about 25% by weight and said polyamide is a nylon.
 16. The bag of claim 15 wherein said polyethylene polymer is a copolymer of ethylene and less than 10% by weight of an alpha-olefin based on said polymer.
 17. The bag of claim 16 wherein the alpha-olefin has from about 3 to about 10 carbon atoms.
 18. The bag of claim 17 wherein said alpha-olefin is a member selected from the group consisting of 1-butene; 1-hexene; 2-ethyl; 1-hexene and 1-octene.
 19. The bag of claim 14 wherein said metal salt of a fatty acid is at least one member selected from the group consisting of alkali metal, alkaline earth metal and zinc salts of a C₁₂ -C₁₈ fatty acid.
 20. The bag of claim 19 wherein said metal salt is a member selected from the group consisting of calcium and zinc salts of a C₁₂ -C₁₈ fatty acid.
 21. The bag of claim 20 wherein said salt is a member selected from the group consisting of calcium and zinc stearate.
 22. The bag of claim 21 wherein said salt is calcium stearate.
 23. The bag of claim 14 wherein said adhesion promoting proportion is from about 1000 to about 7500 parts per million of said first layer.
 24. The bag of claim 23 wherein said proportion is from about 1500 to about 5000 parts per million of said first layer.
 25. The bag of claim 24 wherein said proportion is about 2000 parts per million of said first layer.
 26. The bag of claim 14 wherein said polyolefin is a copolymer of ethylene and a member selected from the group consisting of 1-butene; 1-hexene, 2-ethyl; 1-hexene and 1-octene; said ionomer is a metal-containing ionic copolymer of an olefin and an ethylenically unsaturated monocarboxylic acid; and said polyamide is a nylon. 